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Title: Towards the total synthesis of (-)-sparteine and other lupin alkaloids & new chiral catalysts for asymmetric epoxidations
Author: Pop, Ionut-Alexandru
ISNI:       0000 0004 5347 9748
Awarding Body: University of Southampton
Current Institution: University of Southampton
Date of Award: 2015
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Synthetic routes towards the total synthesis of (−)-sparteine (1.1) have been investigated. An imino-aldol reaction between different ester enolates and chiral sulfinimines was explored to install two of the stereogenic centres. An N-acylimnium precursor was introduced from a selective imide reduction with LiEt3BH and several cyclisation strategies were investigated to install the two remaining stereocenters. Total synthesis of the bicyclic lupin alkaloid (−) lamprolobine (1.107) has been completed in 21% yield over 12 steps as part of the synthetic studies towards 1.1. The target molecule was assembled using a diastereoselective imino aldol reaction and radical deoxygenation as key transformations in the synthesis. The stereochemistry of the major syn product of the imino-aldol reaction was confirmed by single crystal X-ray crystallography. In addition to this, several chiral acyclic α-ketoamides and cyclic α-ketoamides have been synthesised and evaluated in ketone mediated epoxidation of olefins. Despite the modest enantiomeric excesses (ee < 10%) achieved, it was shown that these α- ketocarboxylic acid derivatives are capable of efficient epoxidation at low catalyst loadings.
Supervisor: Brown, Richard Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry